CN103804831B

CN103804831B - Anti-slippery RX and preparation technology

Info

Publication number: CN103804831B
Application number: CN201410018005.7A
Authority: CN
Inventors: 郝洪; 李庆石
Original assignee: SHANDONG TIANYUAN CHEMICAL CO Ltd
Current assignee: SHANDONG TIANYUAN CHEMICAL CO Ltd
Priority date: 2014-01-15
Filing date: 2014-01-15
Publication date: 2016-08-31
Anticipated expiration: 2034-01-15
Also published as: CN103804831A

Abstract

The present invention provides a kind of anti-slippery RX and preparation technology, and softening agent comprises the raw material of following parts by weight: naphthenic oil: 70-90 part, alkenes hybrid resin: 10-30 part, aluminum chloride: 0.1-1.0 part.Its preparation technology follows the steps below: 1) naphthenic oil is warmed to 120-160 DEG C, is subsequently adding catalyst aluminum chloride, stirs 20-50 minute, when constant temperature 150-155 DEG C, adds alkenes hybrid resin, stirs 240-360 minute；2) mixing raw material heats and maintains constant temperature 160-170 DEG C, stir 120-160 minute, then cool to 40-60 DEG C, constant temperature stratification, collect upper layer substance and be anti-slippery RX.The anti-slippery RX of the present invention has the advantage of environment-friendly aromatic oil and environmental protection naphthenic oil properties concurrently, has good wet-sliding resistant performance, relatively low resistance to rolling, good anti-wear performance.

Description

Anti-slippery RX and preparation technology

(1) technical field

The present invention relates to a kind of RX, a kind of anti-slippery RX and preparation technology.

(2) background technology

In the course of processing of rubber, the consumption of RX is the third-largest raw material being only second to rubber, carbon black.Glue Material adds the plasticity that can not only improve sizing material after RX, reduce the viscosity of sizing material and mixing time temperature, save refining The power consumption of glue, improves dispersion and the mixing of other compounding ingredients, to rolling and having extruded lubrication, but also can reduce The hardness of vulcanizate, improves the performance (such as hot strength, percentage elongation, tolerance to cold etc.) of vulcanizate.Therefore RX is rubber In the course of processing of glue product, tool is of great significance.

Petroleum RX is the side-product in petroleum refining process, has that bating effect is good, abundance, cost Cheap feature, all can apply in natural rubber and general purpose synthetic rubber.Adding at rubber product (particularly tire) at present The softening agent almost all used during work is petroleum RX.Petroleum RX is mainly by aromatic hydrocarbons, ring Alkane, alkane etc. form.The DAE oil that aromatic hydrocarbons (CA) content is of a relatively high is mainly used in the process of manufacture of tire The NAP oil of a relatively high with environment-friendly type TDAE oil (solvent refining DAE oil) and cycloalkane (CN) content and environment-friendly type NAP oil are (molten Agent refines NAP oil).Specify according in european union directive 2005/69/EC: direct plunge into the interpolation oil in market or for manufacturing tire Interpolation oil should meet techniques below parameter: benzopyrene (BaP) content should be less than 1mg/kg, simultaneously 8 kinds of PAHs (BaP, BeP, BaA, CHR, BbFA, BjFA, Bk-FA, DBAhA) total content should be less than 10mg/kg.If according to institute of petroleum in britain's standard IP346:1998 " untapped base oil and the condensed-nuclei aromatics content-dimethyl sulfoxide refraction index without asphalt component oil product Method " test PCA mass content little 3%.Undesirable must not put on market and for tire or the life of tyre element Produce.After instruction is promulgated, environment-friendly type aromatic naphtha (TDAE oil) and environment-friendly type naphthenic oil (NAP oil) become the main of RX Development direction.According to TDAE oil and the comparative analysis of NAP oil, substantial amounts of test data shows the processes of TDAE oil Energy, physical and mechanical properties and wet-sliding resistant performance are better than NAP oil.And the resistance to rolling of NAP oil, vitrification point are less than TDAE Oil.Two kinds of products all have shortcoming.

(3) summary of the invention

The technical assignment of the present invention is for the deficiencies in the prior art, it is provided that a kind of anti-slippery RX and preparation work Skill.

The technical solution adopted for the present invention to solve the technical problems is:

Anti-slippery RX, it comprises the raw material of following parts by weight:

Naphthenic oil: 70-90 part, alkenes hybrid resin: 10-30 part, aluminum chloride: 0.1-1.0 part.

Anti-slippery RX, it comprises the raw material of following preferred weight number:

Naphthenic oil: 75-85 part, alkenes hybrid resin: 15-25 part, aluminum chloride: 0.4-0.7 part.

Described alkenes hybrid resin refers to the hybrid resin of terpenes and cyclopentenes.

A kind of preparation technology of anti-slippery RX, this preparation technology follows the steps below:

1) naphthenic oil of 70-90 part is warmed to 120-160 DEG C, is then added thereto to catalyst aluminum chloride 0.1- 1.0 parts, stir 20-50 minute, when temperature maintains constant temperature 150-155 DEG C, add alkenes hybrid resin 10-30 part, stirring 240-360 minute；

2) mixing raw material heated and maintain temperature between constant temperature 160-170 DEG C, stirring 120-160 minute, then drop Temperature to 40-60 DEG C, constant temperature stands 120-180 minute, layering, after getting rid of lower floor's layering thing, collects upper strata layering thing and is product Anti-slippery RX.

The anti-slippery RX of the present invention and preparation technology compared with prior art, produced by provide the benefit that:

1) advantage that the anti-slippery RX of the present invention has had TDAE oil and NAP oil properties concurrently.

2) the every physical and mechanical properties before and after ageing of rubber is essentially identical with TDAE oil, is better than NAP oil.

3) tn δ 0 DEG C value is higher than TDAE oil and NAP oil, and tn δ 60 DEG C value is essentially identical with TDAE oil.Vitrification point is less than TDAE oil and NAP oil.The anti-slippery RX of the present invention has a good wet-sliding resistant performance, and relatively low resistance to rolling is good Good anti-wear performance, the good antiskid performance particularly being had on ice and snow road be advantageous to tire export to Northern Europe and Cold district uses.

4) the anti-slippery RX not only price of the present invention is less than TDAE oil, and density is also below TDAE oil, uses Its sizing material density produced reduces substantially, can effectively reduce Tire production cost.

5) it is far smaller than TDAE oil due to pour point and viscosity, user can be greatly reduced for ease of conveying for equipment, pipe The energy expenditure of road heating and thermal insulation.Owing to having the advantage on TDAE oil and NAP oil properties concurrently, it is used alone the anti-of the present invention Wet and slippery RX not only can meet the requirement of properties, and can reduce use TDAE oil, NAP oil two kinds oily time Existing storage, the expense of production management and the loss caused because accidentally using.

(4) accompanying drawing explanation

Fig. 1 is the Mooney viscosity block diagram of the present invention and domestic and international tire enterprise；

Fig. 2 is the mooney scorch block diagram of the present invention and domestic and international tire enterprise；

Fig. 3 is the vulcameter T90 value block diagram of the present invention and domestic tire enterprise；

Fig. 4 is the hot strength block diagram of the present invention and domestic and international tire enterprise；

Fig. 5 is the 300% stretching strength block diagram of the present invention and domestic and international tire enterprise；

Fig. 6 is the elongation at break block diagram of the present invention and domestic and international tire enterprise；

Fig. 7 is 60 DEG C of tn δ-value block diagrams of the present invention and domestic and international tire enterprise；

Fig. 8 is 0 DEG C of tn δ-value block diagram of the present invention and external tire enterprise；

Fig. 9 is the Akron abrasion block diagram of the present invention and domestic tire enterprise；

Figure 10 is the density block diagram of the present invention and domestic tire enterprise.

(5) detailed description of the invention

Anti-slippery RX and preparation technology to the present invention are described in detail below below in conjunction with the accompanying drawings.

Embodiment 1:

Anti-slippery RX, it comprises the raw material of following parts by weight:

Naphthenic oil: 70 parts, alkenes hybrid resin: 20 parts, aluminum chloride: 1.0 parts.

1) naphthenic oil of 70 parts is warmed to 120-160 DEG C, is then added thereto to catalyst aluminum chloride 1.0 parts, stirs Mix 20-50 minute, when temperature maintains constant temperature 150-155 DEG C, add alkenes hybrid resin 20 parts, stir 240-360 minute；

Embodiment 2:

Anti-slippery RX, it comprises the raw material of following parts by weight:

Naphthenic oil: 80 parts, alkenes hybrid resin: 30 parts, aluminum chloride: 0.1 part.

1) naphthenic oil of 80 parts is warmed to 120-160 DEG C, is then added thereto to catalyst aluminum chloride 0.1 part, stirs Mix 20-50 minute, when temperature maintains constant temperature 150-155 DEG C, add alkenes hybrid resin 30 parts, stir 240-360 minute；

Embodiment 3:

Anti-slippery RX, it comprises the raw material of following parts by weight:

Naphthenic oil: 90 parts, alkenes hybrid resin: 10 parts, aluminum chloride: 0.5 part.

1) naphthenic oil of 90 parts is warmed to 120-160 DEG C, is then added thereto to catalyst aluminum chloride 0.5 part, stirs Mix 20-50 minute, when temperature maintains constant temperature 150-155 DEG C, add alkenes hybrid resin 10 parts, stir 240-360 minute；

The contrast test situation of the anti-slippery RX of the present invention is as follows:

1, this case test

1.1, raw material

SSBR-5025-2 imported product；BR9000, Sinopec yanshan petrochemical limited company product；High score Dissipate white carbon 1165MP, Rhodia Inc's product；Silane coupler, Nanjing Pin Ning coupling agent company limited product；No. 1-environmental protection Type naphthenic oil (NAP oil), middle sea asphaltic products；No. 2-environment-friendly type anti-slippery RX TY-18, Shandong Tian Yuan chemical industry is limited Products；No. 3-environment-friendly type aromatic naphtha Viavatec500 (TDAE oil), Germany's Chinese sage's product.Other raw material is tire Conventional raw material.

1.2, test recipe

Passenger tire crown formula

1.3, main experimental equipment and instrument: X (K)-160 type mill, Wuxi rubber machinery plant product；1.7L Ben Baili Banbury, Japanese kobe steel Products；AI-8000S type electronic tensile machine, TaiWan, China high ferro Science and Technology Co., Ltd. Product；Ageing oven, Shanghai experimental apparatus head factory product；MDR2000 type is without rotor vulcameter and MV2000 type Mooney viscosity Instrument, Alpha Technologies Corp. Ltd. of U.S. product；AB1500 type Akron abrasion machine, Shanghai Hua Jisi factory product；SDTA861e Type DMA Dynamic Viscoelastic testing machine, Switzerland Mei Teletuo benefit Products.

1.4, prepared by sample

Sizing material uses two sections of calendering process mixing.One section mixing is carried out in 1.7L Ben Baili banbury, and charging sequence is Rubber → zinc oxide → stearic acid → protection wax → age resistor → white carbon → softening agent → bottom sheet → park 4h；Two-stage mixing exists Carry out in mill, charging sequence be one section of elastomeric compound → accelerator → sulfur → thin logical → bottom sheet → cool down → park.

1.5, performance test

The stress at definite elongation of GB/T528-1998 vulcanizate, hot strength and elongation at break GB/T529-1999 tearing strength

GB/T1689-1998 wear hardness

GB/T3512-2001 ageing properties

Remaining properties is all according to country or the test of industry respective standard.

2, this case test data and discussion

2.1, the physicochemical property of environmental protection softening agent (oily)

The physicochemical property of table 1 environmental protection softening agent (oily)

As it can be seen from table 1 density: No. 3 > No. 1 > No. 2, from composition analysis arene content 3 > No. 1 > No. 2, volume cost Advantage 2 > No. 1 > No. 3.Kinematic viscosity: No. 2 minimums, makes macromolecular chain be more easily sliding flexibility and the flowing increasing sizing material Property, the beneficially reduction of compound viscosity.Aniline point: No. 2 > No. 1 > No. 3 traditional performances meeting oil product.Carbon type analysis: the CA of No. 3 Being worth its arene content the highest more, CP value its linear paraffin minimum and isoparaffin content are less, the CA value of No. 2 its aromatic hydrocarbons minimum Content is minimum, and in conjunction with parametric synthesis analyses such as kinematic viscosity, index of refraction and pour points, the reason that No. 2 CP values are high is containing substantial amounts of Isoparaffin and part mix what ring-type alkenes hydrocarbon was caused, and the intermiscibility of this composition and general purpose rubber is worked as with TDAE oil phase, excellent In NAP oil.Three kinds of oily PCA content≤3%, PAHs≤10ppm meets European Council Regulation requirement.

2.2, vulcanization characteristics test data

Table 2 vulcanization characteristics test data

From table 2 it can be seen that Mooney viscosity: No. 3 > No. 1 > No. 2, the bating effect of No. 2 is optimum, makes compounding ingredient be easier to mix Enter, it is simple to roll, the technique such as extrusion.Three kinds of oil of time of scorch are essentially identical.Three kinds of oily ML and Mooney viscosity base in vulcanization characteristics This is consistent, and MH, T10, T90 are essentially identical.

2.3, physical and mechanical properties test data

Table 3 physical and mechanical properties test data

Note: DMA tests, temperature range-20 DEG C～80 DEG C；Active force 5N；Amplitude 3 μm；Frequency 10HZ

From table 3 it can be seen that density: No. 2 minimums, volume cost is minimum.300% stretching strength: No. 2 are slightly less than 1 Number and No. 3, elongation at break: No. 2 be slightly larger than No. 1 and No. 3, illustrate No. 2 preferable with the intermiscibility of general purpose rubber and bating effect. Akron abrasion: No. 2 are slightly less than No. 1 and No. 3, owing to No. 2 intermiscibilities good with general purpose rubber contribute to carrying of anti-wear performance High.0 DEG C of tan δ-value: No. 2 >=No. 3 > No. 1, it is known that No. 2, the anti-slippery of No. 3 preferable, No. 1 is poor.60 DEG C of tan δ-value: No. 2=3 Number > No. 1, it is known that No. 2, the resistance to rolling of No. 3 is more than No. 1.The DMA result of No. 1 and No. 3 with the result of the test done in the past has been Entirely it coincide.Before and after other are aging, properties is essentially identical.

3, the practical riding crown test data of domestic and international well-known tire enterprise and discussion

3.1, vulcanization characteristics test data

Table 4 vulcanization characteristics test data

From table 4, it can be seen that in the case of test recipe, experimental condition are different, absolute with each item data of table 2 Though value differs, but the feature of its data is identical.

3.2, physical and mechanical properties test data

Table 5 physical and mechanical properties test data

As can be seen from Table 5, the density before and after aging: No. 2 minimums, volume cost is minimum.Acker before and after aging Grand abrasion: No. 3 > No. 1 > No. 2, No. 2 intermiscibilities good with general purpose rubber contribute to the raising of anti-wear performance.Pressure before and after aging No. 2 minimums of compression deformation, illustrate that No. 2 have good intermiscibility and interior lubricity with general purpose rubber, produce lower heat and rolling Dynamic resistance.0 DEG C of tan δ-value: No. 2 > No. 3 > No. 1, wet-sliding resistant performance 2 is best, and No. 1 is worst.60 DEG C of tan δ-value: No. 2≤No. 1 < 3 Number, No. 2, the resistance to rolling of No. 1 is less than No. 3.The DMA result of No. 1 and No. 3 is to fit like a glove with the result of the test done in the past 's.Vitrification point: No. 2 are minimum, to reducing intermolecular mutual active force, the motor capacity effect increasing macromole is more preferable, Owing to the reduction of vitrification point can be effectively improved the tolerance to cold of rubber and anti-wear performance particularly at the ice snow covered pavement of cold district There is on face more preferable anti-wear performance and antiskid performance.Before and after other are aging, properties is essentially identical.

4, this case test and the comparison of domestic and international tire enterprise main experimental data characteristics

4.1, Mooney viscosity ML1+4100 DEG C

(see Fig. 1)

In the case of test recipe and experimental condition are different, No. 2 Mooney viscosities of common trait are minimum, and No. 3 are the highest, and 1 Number placed in the middle on the upper side.The bating effect of No. 2 is optimum, is more beneficial for the techniques such as calendering, extrusion

4.2, mooney scorch t5, min

(see Fig. 2)

Common trait is that No. 3 mooney scorches are longer, and No. 1 essentially the same with No. 2, can be by the adjustment of vulcanizing system in formula Solve.

4.3, vulcameter T90, min

(see Fig. 3)

Common trait is that vulcameter T90 value is essentially identical, fluctuates the least.

4.4, hot strength, MPa

(see Fig. 4)

Common trait be No. 2 slightly larger than No. 1 and No. 3, No. 1 is essentially identical with No. 3, and three kinds of oil affects base to hot strength As Ben.

4.5,300% stretching strength, MPa

(see Fig. 5)

Common trait be No. 3 slightly larger than No. 1 and No. 2, No. 1 is essentially identical with No. 2, and three kinds of oil affects base to hot strength As Ben.No. 1 basically identical with the most of test data feature done in the past with the test data of No. 3.

4.6, elongation at break, %

(see Fig. 6)

Common trait 2 is bigger；No. 1 placed in the middle；No. 3 less, with 300% stretching strength；Mooney viscosity is consistent substantially.

4.7,60 DEG C of tn δ-value

(see Fig. 7)

Common trait 3 is higher, and resistance to rolling is maximum, No. 2 >=No. 1, in the case of resistance to rolling is essentially the same, and No. 1 summary Low.

4.8,0 DEG C of tn δ-value

(see Fig. 8)

Common trait 2 is higher, and anti-slippery is best, No. 3 > No. 1, No. 1 anti-slippery is worst, the anti-slippery of No. 3 and 1 In the case of number basically identical slightly biased low.

4.9, Akron abrasion, cm3/1.61km

(see Fig. 9)

No. 2 minimums of common trait, abrasion performance is best, and No. 3 >=No. 1, abrasion performance is basically identical.

4.10, density, g/cm3

(see Figure 10)

No. 2 minimums of common trait, volume cost is minimum, and No. 3 are more than No. 1, and volume cost is the highest.

5, conclusion

Comparison by this case test, the discussion of domestic and international tire enterprise test data and main experimental data characteristics is permissible It is concluded that

5.1, the advantage that the anti-slippery RX of the present invention has had TDAE oil and NAP oil properties concurrently.

5.2, the every physical and mechanical properties before and after ageing of rubber is essentially identical with TDAE oil, is better than NAP oil.

5.3, tn δ 0 DEG C value is higher than TDAE oil and NAP oil, and tn δ 60 DEG C value is essentially identical with TDAE oil.Vitrification point is low In TDAE oil and NAP oil.The anti-slippery RX of the present invention has a good wet-sliding resistant performance, relatively low resistance to rolling, Good anti-wear performance, the good antiskid performance particularly being had on ice and snow road is advantageous to tire and exports to Northern Europe And cold district uses.

5.4, the anti-slippery RX not only price of the present invention is less than TDAE oil, and density is also below TDAE oil, Reduce substantially by its sizing material density produced, can effectively reduce Tire production cost.

5.5, due to pour point and viscosity be far smaller than TDAE oil, can be greatly reduced user for ease of conveying for equipment, The energy expenditure of pipe tracing.Owing to having the advantage on TDAE oil and NAP oil properties concurrently, it is used alone the present invention's Anti-slippery RX not only can meet the requirement of properties, and can reduce use TDAE oil, NAP two kinds of oil of oil Time existing storage, the expense of production management and the loss that causes because accidentally using.

Claims

The most anti-slippery RX, it is characterised in that it comprises the raw material of following parts by weight:

Naphthenic oil: 70-90 part, alkenes hybrid resin: 10-30 part, aluminum chloride: 0.1-1.0 part；Described alkenes hybrid resin is Refer to terpenes and the hybrid resin of cyclopentenes；

Its preparation technology follows the steps below:

1) naphthenic oil of 70-90 part is warmed to 120-160 DEG C, is then added thereto to catalyst aluminum chloride 0.1-1.0 part, Stir 20-50 minute, when temperature maintains constant temperature 150-155 DEG C, add alkenes hybrid resin 10-30 part, stir 240-360 Minute；

2) mixing raw material heated and maintain temperature between constant temperature 160-170 DEG C, stirring 120-160 minute, then cool to 40-60 DEG C, constant temperature stands 120-180 minute, layering, after getting rid of lower floor's layering thing, collects upper strata layering thing and is product moisture-resisting Sliding RX.
Anti-slippery RX the most according to claim 1, it is characterised in that it comprises the former of following parts by weight Material:

Naphthenic oil: 75-85 part, alkenes hybrid resin: 15-25 part, aluminum chloride: 0.4-0.7 part.
3. the preparation technology of an anti-slippery RX as claimed in claim 1, it is characterised in that: this preparation technology be by Carry out according to following steps:

1) naphthenic oil of 70-90 part is warmed to 120-160 DEG C, is then added thereto to catalyst aluminum chloride 0.1-1.0 part, Stir 20-50 minute, when temperature maintains constant temperature 150-155 DEG C, add alkenes hybrid resin 10-30 part, stir 240-360 Minute；

2) mixing raw material heated and maintain temperature between constant temperature 160-170 DEG C, stirring 120-160 minute, then cool to 40-60 DEG C, constant temperature stands 120-180 minute, layering, after getting rid of lower floor's layering thing, collects upper strata layering thing and is product moisture-resisting Sliding RX.